Treatment of cellulose derivatives



Patented Jan. 12, 1932 UNITED STATES PATENT OFFICE GEORGE HOLLAND ELLIS, OF SPONDON, NEAR DERBY, ENGIAND, ASSIGNOR TO OELANESE CORPORATION OF AMERICA, A CORPORATION OF DELAWARE TREATMENT OF CELLULOSE DERIVATIVES No Drawing. Application filed September '7, 1926, Serial No. 134,138, and in Great Britain April 10, Isa-6.

This invention relates to the dyeing, printing or stencilling of artificial yarns, threads, filaments, fabrics, films or other products made of or containing cellulose acetate.

I have now found that particularly useful and desirable results may be obtained by the employment of a solubilizing agent or agents consisting of or comprising a sulpho-aroinatic ricinoleic acid or a-salt thereof, that is to say a body which is capable of being obtained by the treatment of a mixture of castor oil and an aromatic compound, for example benzene, phenol or naphthalene, with sulphuric acid; or asalt of such a body, for instance the alkali or ammonium salt.

Accordingly the present invention consists in the dyeing, printing, or stencilling of cellulose acetate or goods containing the same with any insoluble or relatively insoluble colouring matters or organic compounds having aflinity for cellulose acetate or capable of colouring the same, in the form of soluble or more soluble modifications prepared by treatment with solubilizing agents consisting of or comprising one or more bodies being sulpho-aromatic ricinoleic acids, for example sulpho-benzcne ricinoleic acid, sulplio-phenol ricinoleic acid, or sulpho-naphthalene ricinoleic acid; or salts of such bodies, for instance the alkali or ammonium salts of such bodies.

The (lyebaths for applying the colouring matters or compounds solubilized according to the present invention may be acid, neutral,

or alkaline and it is also found that good results may be obtained even if hard water be employed in making up the dyebath.

Any insoluble or relatively insoluble colouring matter or compound having affinity for cellulose acetate may be employed and the following may be instanced, though it is to be understood that such examples are not intended to limit the invention, which contemplates as stated above the employment of any insoluble or relatively insoluble colour ing matter or compound having the requisite aflinity. Thus I may employ the colouring matters or organic compounds more particularly referred to in my previous British specification No. 219349, and U. Patent No. 1,618,418, for instance non-sulphonated or other insoluble or relatively insoluble derivatives of the fazo class, simple or amino bases (e. g. para nitraniline, meta nitraniline, benzidine, dianisidine, dimethyl aniline, alpha naphthylamine or diphenylamine) for application for dyeing or colouring the cellulose acetate by the azoic or development process, unreduced indophenols (aryl or substituted aryl benzoor naphthaquinone monoimides), or insoluble or relatively insoluble colouring matters of the following classes: Polyaryl methane, oxazine, azine, thiazine, unreduced indigoid or basic derivatives of the anthraquinone series; insoluble or relatively insoluble pyrazolone derivatives e. g. unsulphonated azo derivatives of pyrazolone compounds, such as are referred to in my previous British specification No. 224681 and in my S.- Patent No. 1,600,277; unreduced vat dyestuffs of the anthraquinone series as referred to in my previous British specification No. 227188 and in my U. S. Patent No. 1,641,965, for instance those marketed under the registered trade marks Indanthrene, Cibanone, Algol and Helindone; insoluble or relatively insoluble nitroderivatives of diarylamines such as those referred to in my previous British specification No. 2379-13 and in my U. S. Patent No. 1,618,415; insoluble or relatively insoluble acidyl derivatives of aminoanthraquinones or of substituted aminoanthraquinones, containing one or more aliphatic acidylamino groups, such as those referred to in my application for British Patout No. 26576 of 1925 and my U. S. application S. No. 98,614 of 30 March 1926; insoluble or relatively insoluble colouring matters or compounds of the stilbene group containing no sulpho groups in their constitution,

such as those referred to in my application for British Patent No. 7317 of 1925 and in my U. S. application S. No. 93,77 9 of 10th March 1926.

The colouring matters or compounds for use in the presentinvention will usually contain no strongly acidic groups such as the sulpho group, and when basic colouring matters or compounds are employed they are always used in the form of the base and not in the form of salts such as the hydrochloride.

The solubilization may be effected by mixing or grinding the insoluble or relatively insoluble colouring matters or compounds with one or more of the solubilizing agents of the present invention, in presence or absence of water,if desired in presence of comparatively large quantities of water with subsequent concentration,-and heating if necessary, the solubilized modifications being filteredif required before addition to the dyebaths or other preparations for dyeing or otherwise colouring the goods.- The dyeing,

printing or stencilhng may be effected in the usual manner.

If the colouring matter or compound contains diazotizable amino groups, it may be diazotized and developed on the material to form a further dyestutf or dyestuffs.

When dyeings or colourings are to be produced by the azoic process the insoluble or relatively insoluble component (whether base or developer or both) may be solubilized with the agents of the present invention and the dyeing and developing conducted as usual. f

Other colouring matters which are not deleteriously affected by the solubilizing agents of the present invention may if desired, be

dyed on the material together with the colouring matters or compounds treated according to the present invention.

Mixed goods may be dyed or otherwise coloured in uniform or contrasting effects with or without employment of other dyestufl's or components according, to the character of the nonacetate portion of the goods, saidother dyestuffs being applied before, after, or, if not deleteriously aii'ccted thereby, together with the insoluble dyestufl's or compounds treated according to the present invention.

The solubilizing agents of the present invention may be prepared in any known or suitable way. The following Example A illilllstrates one convenient method of preparing t em.

Example A.Method of preparing the solubilizing agent.

172 lbs. of sulphuric acid (monohydrate) are charged into a jacketed mixer, 60 lbs. of

naphthalene added, and 60 lbs. of castor oil run in during one hour, cooling water being run through the jacket so that the temperature rises only to 2530 C.

The water is then run off from the jacket,

hours, after which it is allowed to cool to a moderate temperature. It is now blown into l30gallons of 20% brine, stirred well and allowed to settle. The brine is now drawn off and the layer of oil given two further similar treatments, after which the separated oil is mixed with 20-30 lbs. of hot water, neutralized with 30% caustic soda solution, and finally made up to 312 lbs. by addition of water.

The following are'some examples of the manner in which the invention may be performed it being understood that these are given only by way of illustration and can be varied widely without departing from the invention. i

E mample 1.-To dye 100 lbs. of cellulose acetate yarn in hank form a bright golden yellow colour 1 lb. of 4 hydroxy 2 2 4 dinitrodiphenylamine is ground in a suitable apparatus with 3 lbs. of sulpho-naphthalene ricinoleic acid, sodium salt, prepared as in Example A, and water added to make to 10 lbs.

The paste thus obtained is treated with 10 gallons of boiling water and added to a dyebath containing 300 gallons of soft water in which have been dissolved three pounds of olive oil soap. The well scoured yarn is now entered and the temperature of the bath raised during of an hour to C. and maintained at this temperature a further of an hour. The yarn,.which is now dyed a full golden yellow colour is washed off in soft water, and may be dried or otherwise treated as desired. I

Example 2.To dye 100 lbs. of cellulose acetate yarn in hank form a full yellow shade 1 lb. of alpha acetylamino anthraqumone is ground to a fine powder, and added to 4 lbs. of neutral sodium sulpho naphthalene ricinoleate prepared as in Example A. The whole is now heated to 7580 C. with stirring till as homogeneous as possible, diluted to 10 gallons with boiling water, and added to the dyebath containing 300 gallons of.

ordinary tap water. The goods are now entered, the temperature raised to 7580 in A; of an hour and maintained at thls degree for of an hour. The goods, WhlCh are now dyed a full -greenish yellow are washed off and may be dried or otherwise treated as desired.

Ewample 3.To dye 100 lbs. of cellulose acetate yarn in hank form a pure blue shade 1% lbs. of the indophenol obtained by 0x1- dizing p. amino diethylaniline and alpha naphtholin alkalinesolution (1 p. diethylamino phenyl 4: naphthoquinone monoimide) are reduced to a tine state of division and stirred at a moderate temperature into 5 lbs.

of neutral sodium sulpho naphthalene ricinoleate prepared as in Example A. lVhen as homogeneous as possible the dispersion is diluted with 10 gallons of warm water and poured through a filter cloth into a dyebath containing 300 gallons ofwater. The goods are now entered and dyeing is carried out as in Examples 1 and 2. The goods which are dyed a full pure blue shade, are well washed off and may now be dried or otherwise treated as desired.

Example 4.To dye 100 lbs. of wool-cellulose acetate mixed goods in hank forms Cellulose acetate, yellow.

Wool, red.

Ratio wool-cellulose acetate :-2 1.

lb. of anilineazo-1:pl1enyl-3: methyl- 5 pvrazolone is dispersed in 2 lbs. of sodium sulpho naphthalene ricinoleate (prepared as in Example A) by grinding or other suitable means, diluted to 5 gallons with boiling water. and added to a 300 gallon dyebath in which has previously been dissolved 1% lbs. of A20 Rhodine 2G. (Colour index No. 31). The scoured goods are now entered and the temperature raised gradually, during of an hour to 7 5 C. and maintained for a further of an hour. Exhaustion is assisted by the addition of 3 lbs. of acetic acid during of an hour intervals at 7 075 C. The goods which, are now dyed the requisite shades are washed off well. and may now be dried or otherwise treated as desired.

Example 5.To dye a full bluish black on 100 lbs. of cellulose acetate yarn in hank form 2 lbs. of benzene azo alpha naphthylamine are dispersed in 8 lbs. of sodium sulpho naphthalene ricinoleate prepared as in Example A, and applied to the cellulose acetate yarn by the methods illustrated in Examples 1 and E2. The goods which are dyed a full golden shade. are well washed off and are now ready for the diazotization bath.

Diazotz'zatz'on 4 lbs. of beta oxynaphthoic acid are dissolved in water containing 1 lb. of caustic soda, 20 lbs. of sodium sulpho naphthalene ricinoleic acid-prepared as in Example A are and the temperature then slowly raised to 60 C. being maintained a further- 4 of an hour at thistemperature.

The goods are now lifted, rinsed, soaped for 10 minutes in a ,1 soap solution at "45 C. and well washed off.

They are dyed a full bloomy black and may now be dried or otherwise treated as desired.

The term dyeing in the appended claimsis intended to include printing and stencilling, whilethe term relatively water-insoluble organic compounds capable of colouring cellulose acetate is to be understood to include any insoluble or relatively insoluble colouring matter or organic compound having aifinity for cellulose acetate orcapable of colouring the same or anV component (base ordeveloper) capable of application by the azoioc or development process.

What I claim and desire to secure by Letters Patent is v 1. Process for dyeing materials comprising cellulose acetate, comprising applying thereto aqueous dispersions of relatively water-insoluble organic compounds capable of coloring cellulose acetate prepared by pretreating the compound-s with a solubilizing agent comprising a compound selected from the group consisting of sulpho-aromatic ricinoleic acids and their soluble salts.

2. Process for dyeing materials comprising cellulose acetate, comprising applying thereto aqueous dispersions of relatively water-insoluble organic compounds capable of coloring cellulose acetate prepared by pre- 3. Process'for dyeing materials comprising cellulose acetate, comprising applying thereto aqueous dispersions of relatively water-insoluble organic compounds capable of coloring cellulose acetate, prepared by pretreating the compounds with a solubilizing agent comprising a sodium salt of a sulphoaromatic ricinoleic acid.

4. Process for dyeing materials comprising cellulose acetate, comprising applying thereto aqueous dispersions of relatively water-insoluble organic compounds capable of coloring cellulose acetate prepared by pretreating the compounds with a solubilizing agent comprising a compound selected from the group consisting of sulpho-naphthalene ricinoleic acids and their soluble salts.

5. Process for dyeing materials comprising cellulose acetate,-compr1s1ng applying thereto aqueous dispersions of relatively water-insoluble organic compounds capable of coloring cellulose acetate prepared by prenaphthalene ricinoleic acid.

7. Process for dyeing materials comprising cellulose acetate, comprising applying thereto aqueous dispersions of relatively water-insoluble amino compounds prepared by pretreating the compounds witha solubilizing agent comprising a compound selected from the group consisting of sulphoaromatic ricinoleic acids and their soluble salts and thereafter diazotizing and developing on the material.

8. Dyeing preparations comprising relatively water-insoluble organic compounds pretreated with a solubilizing agent comprising a compound selected. from the group consisting of sulpho-aromatic ricinoleic acids and their soluble salts.

9. Dyeing preparations comprising relatively water-insoluble organic compounds pretreated with a solubilizing agent comprising a soluble salt of a sulpho-aromatic ricinoleic acid.

10. Dyeing preparations comprising relatively water-insoluble organic compounds pretreated with a solubilizing agent comprising a soluble salt of a compound selected from the group consisting of sulpho-naphthalene ricinoleic acids and their soluble salts.

'11. Dyeing preparations comprising relatively water-insoluble organic compounds pretreated with a solubilizing agent comprising a sulpho-naphthalene ricinoleic acid.

12. Process for dyeing materials comprising cellulose acetate, comprising applying theretoaqueous dispersions of relatively water-insoluble organic compounds capable of coloring cellulose acetate prepared by pretreating' the compounds with a solubilizing agent comprising a compound selected from the group consisting of sulpho-benzene ricinoleic acids and their soluble salts.

13. Process for dyeing materials comprising cellulose acetate, comprising applying thereto aqueous dispersions of relatively water-insoluble organic compounds capable of coloring cellulose acetate prepared by pretreating the compounds with a solubilizing agent comprising a compound selected from the groupconsisting of sulpho-phenol ricinoleic acids and their soluble salts.

14. Dyeing preparations comprising relatively water-insoluble organic compounds sisting of sulpho-phenol ricinoleic acids and their soluble salts.

In testimony whereof I have hereunto subscribed my name.

GEORGE HOLLAND ELLIS. 

